Abstract: Rosenfeld [Phys. Rev. A 15, 2545 (1977)] noticed that casting transport
coefficients of simple monatomic, equilibrium fluids in specific dimensionless
forms makes them approximately single-valued functions of excess entropy. This
has predictive value because, while the transport coefficients of dense fluids
are difficult to estimate from first principles, excess entropy can often be
accurately predicted from liquid-state theory. Here, we use molecular
simulations to investigate whether Rosenfeld's observation is a special case of
a more general scaling law relating mobility of particles in mixtures to excess
entropy. Specifically, we study tracer diffusivities, static structure, and
thermodynamic properties of a variety of one- and two-component model fluid
systems with either additive or non-additive interactions of the hard-sphere or
Gaussian-core form. The results of the simulations demonstrate that the effects
of mixture concentration and composition, particle-size asymmetry and
additivity, and strength of the interparticle interactions in these fluids are
consistent with an empirical scaling law relating the excess entropy to a new
dimensionless (generalized Rosenfeld) form of tracer diffusivity, which we
introduce here. The dimensionless form of the tracer diffusivity follows from
knowledge of the intermolecular potential and the transport / thermodynamic
behavior of fluids in the dilute limit. The generalized Rosenfeld scaling
requires less information, and provides more accurate predictions, than either
Enskog theory or scalings based on the pair-correlation contribution to the
excess entropy. As we show, however, it also suffers from some limitations,
especially for systems that exhibit significant decoupling of individual
component tracer diffusivities.